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991.
Marion N Carlqvist P Gealageas R de Frémont P Maseras F Nolan SP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(22):6437-6451
The [(NHC)AuI]-catalyzed (NHC=N-heterocyclic carbene) formation of alpha,beta-unsaturated carbonyl compounds (enones and enals) from propargylic acetates is described. The reactions occur at 60 degrees C in 8 h in the presence of an equimolar mixture of [(NHC)AuCl] and AgSbF6 and produce conjugated enones and enals in high yields. Optimization studies revealed that the reaction is sensitive to the solvent, the NHC, and, to a lesser extent, to the silver salt employed, leading to the use of [(ItBu)AuCl]/AgSbF6 in THF as an efficient catalytic system. This transformation proved to have a broad scope, enabling the stereoselective formation of (E)-enones and -enals with great structural diversity. The effect of substitution at the propargylic and acetylenic positions has been investigated, as well as the effect of aryl substitution on the formation of cinnamyl ketones. The presence or absence of water in the reaction mixture was found to be crucial. From the same phenylpropargyl acetates, anhydrous conditions led to the formation of indene compounds via a tandem [3,3] sigmatropic rearrangement/intramolecular hydroarylation process, whereas simply adding water to the reaction mixture produced enone derivatives cleanly. Several mechanistic hypotheses, including the hydrolysis of an allenol ester intermediate and SN2' addition of water, were examined to gain an insight into this transformation. Mechanistic investigations and computational studies support [(NHC)AuOH], produced in situ from [(NHC)AuSbF6] and H2O, instead of cationic [(NHC)AuSbF6] as the catalytically active species. Based on DFT calculations performed at the B3LYP level of theory, a full catalytic cycle featuring an unprecedented transfer of the OH moiety bound to the gold center to the C[triple chemical bond]C bond leading to the formation of a gold-allenolate is proposed. 相似文献
992.
Marchand P Griffe L Caminade AM Majoral JP Destarac M Leising F 《Organic letters》2004,6(8):1309-1312
The functionalization of phosphorus-containing dendrimers was easily achieved through thioacylation reactions involving new dendrimers capped with dithioester end groups and various functionalized amines. These reactions were successfully applied to the first generation (12 end groups) and the third generation of the dendrimer (48 end groups) and allowed their functionalization by various primary or secondary amines, alcohols, glycols, and azides. [reaction: see text] 相似文献
993.
994.
Jürg?Fr?hlichEmail author Zhou?Gang Avy?Soffer 《Communications in Mathematical Physics》2012,315(2):401-444
We study the motion of a heavy tracer particle weakly coupled to a dense ideal Bose gas exhibiting Bose-Einstein condensation. In the so-called mean-field limit, the dynamics of this system approaches one determined by nonlinear Hamiltonian evolution equations describing a process of emission of Cerenkov radiation of sound waves into the Bose-Einstein condensate along the particle’s trajectory. The emission of Cerenkov radiation results in a friction force with memory acting on the tracer particle and causing it to decelerate until it comes to rest.
“A moving body will come to rest as soon as the force pushing it no longer acts on it in the manner necessary for its propulsion.”—— Aristotle 相似文献
995.
Alexander Bendikov Wojciech Cygan Bartosz Trojan 《Stochastic Processes and their Applications》2017,127(10):3268-3290
We consider a random walk which is obtained from the simple random walk by a discrete time version of Bochner’s subordination. We prove that under certain conditions on the subordinator appropriately scaled random walk converges in the Skorohod space to the symmetric -stable process . We also prove asymptotic formula for the transition function of similar to the Pólya’s asymptotic formula for . 相似文献
996.
Marija S. Nikolic Dr. Charlotta Olsson Andrea Salcher Andreas Kornowski Anja Rank Dr. Rolf Schubert Prof. Dr. Andreas Frömsdorf Dr. Horst Weller Prof. Dr. Stephan Förster Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(15):2752-2754
Nanoparticle brushes : Complex nanostructures can be formed by self assembly of amphiphilic CdSe/CdS core–shell nanoparticles that bear a brushlike layer of poly(ethylene oxide) chains. This route is based on controlling the volume fractions of hydrophilic and hydrophobic moieties within the particles and allows the formation of micellar, cylindrical, or vesicular nanoobjects (see picture).
997.
Disassembly Kinetics of Quinone‐Methide‐Based Self‐Immolative Spacers that Contain Aromatic Nitrogen Heterocycles 下载免费PDF全文
Ahmed Alouane Dr. Raphaël Labruère Katherine J. Silvestre Dr. Thomas Le Saux Dr. Frédéric Schmidt Prof. Dr. Ludovic Jullien 《化学:亚洲杂志》2014,9(5):1334-1340
We prepared several pyridine‐ and pyrimidine‐based self‐immolative spacer groups to evaluate the significance of the resonance energy of the spacer aromatic ring on the kinetics of 1,4‐ and 1,6‐elimination reactions, which govern spacer disassembly. Subsequently, we relied on a photoactivation procedure to accurately analyze the disassembly kinetics. Beyond providing new results that are relevant for deriving quantitative structure–property relationships, herein, we demonstrate that pH value can be used as an efficient parameter to finely control the disassembly time of a self‐immolative spacer after an initial activation. 相似文献
998.
Structure and white luminescence of Eu-activated (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66 materials 总被引:1,自引:0,他引:1
The optical properties of Eu-activated (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66 materials have been determined after the structural reinvestigation of the hypothetical Ba 13Al 22Si 10O 66 material on the basis of the Gebert's model. The white fluorescence and phosphorescence of the (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66:Eu series result from the existence of two broad emission bands associated with (8)H-4f(6)5d(1)-->(8)S-4f(7) transitions peaking at 534 and 438 nm, the intensities of which may be tuned at room temperature via the control of the europium concentration and the substitution of Sr for Ba. This suggests the possibility to adjust the emission of the material to white LED requisites. 相似文献
999.
Frédéric Bernicot 《Mathematische Annalen》2011,351(1):1-49
In this work, we study some non-smooth bilinear analogues of linear Littlewood–Paley square functions on the real line. We prove boundedness-properties in Lebesgue spaces for them. Let us consider the functions \({\phi_{n}}\) satisfying \({\widehat{\phi_n}(\xi)={\bf 1}_{[n,n+1]}(\xi)}\) and define the bilinear operator \({S_n(f,g)(x):=\int f(x+y)g(x-y) \phi_n(y) dy}\) . These bilinear operators are closely related to the bilinear Hilbert transforms. Then for exponents \({p,q,r'\in[2,\infty)}\) satisfying \({\frac{1}{p}+\frac{1}{q}=\frac{1}{r}}\) , we prove that
相似文献
$\left\| \left( \sum_{n\in \mathbb{Z}}\left|S_n(f,g) \right|^2 \right)^{1/2}\right\|_{L^{r}(\mathbb{R})}\lesssim \|f\|_{L^p(\mathbb{R})}\|g\|_{L^q(\mathbb{R})}.$
1000.
Broaders KE Pastine SJ Grandhe S Fréchet JM 《Chemical communications (Cambridge, England)》2011,47(2):665-667
Acid-degradable microcapsules were prepared via an interfacial polymerization. Degradation of the thin wall of the capsules leads to all-or-nothing cargo release. The only byproducts of degradation are acetone, and a non-toxic triamide. Proof-of-concept experiments showed that cargo can be delivered to and released in cells. 相似文献